KR102383997B1 - Polysiloxane-polycarbonate copolymer using a mixture of hydroxyl-terminated polysiloxanes and method for preparing the same - Google Patents

Abstract

The present invention relates to a polysiloxane-polycarbonate copolymer using a hydroxyl-terminated polysiloxane mixture and a method for preparing the same, and more particularly, by including the hydroxyl-terminated polysiloxanes of Formulas 1 and 2 as repeating units in a specific weight ratio, these hydroxyl The present invention relates to a polysiloxane-polycarbonate copolymer, which exhibits superior transmittance and low-temperature impact strength, as compared to the case where each of the hydroxy-terminated polysiloxanes is included alone, and is excellent in economical aspect by improving the overall production yield of the raw polysiloxane, and a method for preparing the same.

Description

Polysiloxane-polycarbonate copolymer using hydroxy-terminated polysiloxane mixture and method for preparing the same

The present invention relates to a polysiloxane-polycarbonate copolymer using a hydroxyl-terminated polysiloxane mixture and a method for preparing the same, and more particularly, by including the hydroxyl-terminated polysiloxanes of Formulas 1 and 2 as repeating units in a specific weight ratio, these hydroxyl The present invention relates to a polysiloxane-polycarbonate copolymer, which exhibits superior transmittance and low-temperature impact strength, as compared to the case where each of the hydroxy-terminated polysiloxanes is included alone, and is excellent in economical aspect by improving the overall production yield of the raw polysiloxane, and a method for preparing the same.

Polycarbonate has excellent mechanical properties such as tensile strength and impact resistance, and has excellent dimensional stability, heat resistance, and optical transparency, so it is widely used for industrial purposes. However, polycarbonate has excellent impact resistance at room temperature, but has a weakness in that impact resistance is rapidly reduced at low temperatures.

In order to improve this weakness, research on various copolymers is ongoing, and as a result, polysiloxane-polycarbonate copolymers have been proposed (US Patent Publication No. 2003/0105226).

Polysiloxane-polycarbonate copolymers are known to have relatively good impact resistance at low temperatures. However, the conventional polysiloxane-polycarbonate copolymer requires a high content of siloxane to develop low-temperature impact resistance, and increasing the content of siloxane has a problem of inhibiting the transparency of the polysiloxane-polycarbonate copolymer, so commercial use is limited. is acting as

Accordingly, it is possible to prepare a polysiloxane-polycarbonate copolymer exhibiting excellent transmittance and low-temperature impact strength, and at the same time, the overall production yield of the raw material polysiloxane is improved, and there is a need for the development of excellent technology in terms of economy.

An object of the present invention is to provide a polysiloxane-polycarbonate copolymer that exhibits excellent transmittance and low-temperature impact strength, and is also excellent in economical efficiency by improving the overall production yield of the raw material polysiloxane, and a method for producing the same.

In order to achieve the above technical problem, the present invention provides, as a repeating unit, a hydroxy-terminated polysiloxane represented by the following Chemical Formula 1; Hydroxy-terminated polysiloxane of Formula 2; and a polycarbonate block, wherein a total of 100 parts by weight of the hydroxy-terminated polysiloxanes of Formulas 1 and 2 consists of 1 to 39 parts by weight of the polysiloxane of Formula 1 and 61 to 99 parts by weight of the polysiloxane of Formula 2 Polysiloxane-poly Provided is a carbonate copolymer:

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

R ₁ each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group or an aryl group,

R ₂ each independently represents a hydrocarbon group or a hydroxyl group having 1 to 13 carbon atoms,

R ₃ each independently represents an alkylene group having 2 to 8 carbon atoms,

A represents a substituted or unsubstituted divalent hydrocarbon group containing at least one bond selected from an ester bond, an ether bond, a thioether bond, a ketone bond, or a urethane bond,

l represents an integer of 0 to 4,

m and n each independently represent an integer of 2 to 1,000.

According to another aspect of the present invention, (1) the hydroxy-terminated polysiloxane of Formula 1, the hydroxy-terminated polysiloxane of Formula 2, and the oligomeric polycarbonate are reacted under interfacial reaction conditions to form a polysiloxane-polycarbonate intermediate; and (2) polymerizing the polysiloxane-polycarbonate intermediate using a first polymerization catalyst, wherein a total of 100 parts by weight of the hydroxy-terminated polysiloxanes of Formulas 1 and 2 is 1 to 39 weights of the polysiloxane of Formula 1 A method for preparing a polysiloxane-polycarbonate copolymer is provided, consisting of parts and 61 to 99 parts by weight of the polysiloxane of formula (2).

According to another aspect of the present invention, there is provided a molded article including the polysiloxane-polycarbonate copolymer.

The present invention relates to a polysiloxane-polycarbonate that exhibits excellent transmittance and low-temperature impact strength so that it can be suitably used in molded articles requiring both transparency and low-temperature impact resistance (eg, housings of office equipment and electrical and electronic products, film and sheet products, etc.) It is possible to provide a copolymer, and also improves the overall production yield of the raw material polysiloxane, which is excellent in terms of economical efficiency.

Hereinafter, the present invention will be described in more detail.

Polysiloxane-polycarbonate copolymer of the present invention, as a repeating unit, a hydroxy-terminated polysiloxane represented by the following formula (1); Hydroxy-terminated polysiloxane of Formula 2; and a polycarbonate block, wherein a total of 100 parts by weight of the hydroxy-terminated polysiloxanes of Formulas 1 and 2 consists of 1 to 39 parts by weight of the polysiloxane of Formula 1 and 61 to 99 parts by weight of the polysiloxane of Formula 2.

(A) hydroxy-terminated polysiloxane of formula (1)

The hydroxy-terminated polysiloxane of the following formula (1) included as a repeating unit in the polysiloxane-polycarbonate copolymer according to the present invention has a hydroxyphenyl group at the terminal, and is formed from an ester bond, an ether bond, a thioether bond, a ketone bond or a urethane bond. Hydroxy-terminated polysiloxane compounds comprising one or more selected linkages.

[Formula 1]

In Formula 1,

R ₁ each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group or an aryl group,

R ₂ each independently represents a hydrocarbon group or a hydroxyl group having 1 to 13 carbon atoms,

R ₃ each independently represents an alkylene group having 2 to 8 carbon atoms,

A represents a substituted or unsubstituted divalent hydrocarbon group containing at least one bond selected from an ester bond, an ether bond, a thioether bond, a ketone bond, or a urethane bond,

l represents an integer of 0 to 4,

n each independently represents an integer of 2 to 1,000.

According to one embodiment, in Formula 1,

R ₁ each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

R ₂ each independently represents a hydrocarbon group or a hydroxyl group having 1 to 13 carbon atoms,

R ₃ each independently represents an alkylene group having 2 to 8 carbon atoms,

를 나타내며, 여기서 Y는 X 또는 NH-X-NH이며, 여기서, X는 탄소수 1 내지 20의 선형 또는 분지형 지방족기; 탄소수 3 내지 20의 사이클로알킬렌기; 또는 할로겐 원자, 알킬기, 알콕시기, 아릴기 또는 카르복실기로 치환된 또는 비치환된 탄소수 6 내지 30의 단핵 또는 다핵의 아릴렌기를 나타내며,A is

, wherein Y is X or NH-X-NH, wherein X is a linear or branched aliphatic group having 1 to 20 carbon atoms; a cycloalkylene group having 3 to 20 carbon atoms; or a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms, which is substituted or unsubstituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a carboxyl group,

l represents an integer of 0 to 4,

n each independently represents an integer of 2 to 1,000.

More specifically,

In R ₁ of Formula 1, the halogen atom may be Cl or Br; The alkyl group may be an alkyl group having 1 to 13 carbon atoms, such as methyl, ethyl or propyl; The alkoxy group may be an alkoxy group having 1 to 13 carbon atoms, such as methoxy, ethoxy or propoxy; The aryl group may be an aryl group having 6 to 10 carbon atoms, such as phenyl, chlorophenyl or tolyl;

In R ₂ of Formula 1, the hydrocarbon group having 1 to 13 carbon atoms is an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, an alkenyl group having 2 to 13 carbon atoms, an alkenyloxy group having 2 to 13 carbon atoms, 3 to carbon atoms. A cycloalkyl group of 6, a cycloalkoxy group of 3 to 6 carbons, an aryloxy group of 6 to 10 carbons, an aralkyl group of 7 to 13 carbons, an aralkoxy group of 7 to 13 carbons, an alkaryl group of 7 to 13 carbons, or a carbon number 7 to 13 alkaryloxy groups;

를 나타내며, 여기서 Y가 X 또는 NH-X-NH일 경우, 여기서 X는, 예를 들면, 할로겐 원자로 치환된 또는 비치환된 탄소수 1 내지 20의 지방족기, 주쇄에 산소, 질소 또는 황 원자를 포함하는 탄소수 1 내지 20의 지방족기, 탄소수 3 내지 6의 사이클로알킬렌기, 또는 비스페놀 A, 레소시놀, 히드로퀴논 또는 디페닐페놀로부터 유래될 수 있는 아릴렌기일 수 있으며, 예컨대, X는 하기 화학식 Aa 내지 Ah 중 어느 하나로 나타내어질 수 있다.A in formula 1

, wherein when Y is X or NH-X-NH, where X is, for example, an aliphatic group having 1 to 20 carbon atoms substituted or unsubstituted with a halogen atom, and an oxygen, nitrogen or sulfur atom in the main chain may be an aliphatic group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 6 carbon atoms, or an arylene group that may be derived from bisphenol A, resorcinol, hydroquinone or diphenylphenol, for example, X is represented by the following formulas Aa to It may be represented by any one of Ah.

[Formula Aa]

[Formula Ab]

[Formula Ac]

[Formula Ad]

[Formula Ae]

[Formula Af]

[Formula Ag]

[Formula Ah]

According to one embodiment, the hydroxy-terminated polysiloxane of Formula 1 may be a reaction product of a hydroxy-terminated siloxane of Formula 1a with an acyl compound (ie, hydroxy-terminated siloxane having an ester bond).

[Formula 1a]

In Formula 1a, R ₁ , R ₂ , R ₃ , 1 , and n are the same as defined in Formula 1 above.

The hydroxy-terminated siloxane of Formula 1a is synthesized by, for example, a compound of Formula 1b having a hydroxyl group and a double bond and a compound of Formula 1c containing silicone in a molar ratio of 2:1 using a platinum-based catalyst. can be manufactured.

[Formula 1b]

In Formula 1b, R ₁ and 1 are as defined in Formula 1 above, and k represents an integer of 1 to 7.

[Formula 1c]

In Formula 1c, R ₂ and n are the same as defined in Formula 1 above.

The acyl compound used for preparing the hydroxy-terminated polysiloxane of Formula 1 may have, for example, an aromatic, aliphatic, or mixed structure including both aromatic and aliphatic. When the acyl compound is aromatic or mixed, it may have 6 to 30 carbon atoms, and when aliphatic, it may have 1 to 20 carbon atoms. In addition, the acyl compound may further include a halogen, oxygen, nitrogen or sulfur atom.

In another embodiment, the hydroxy-terminated siloxane of Formula 1 may be a reaction product of the hydroxy-terminated siloxane of Formula 1a with a polyisocyanate compound (ie, a hydroxy-terminated polysiloxane having a urethane bond).

Here, the polyisocyanate compound is, for example, 1,4-phenylenediisocyanate, 1,3-phenylenediisocyanate, or 4,4'-methylenediphenyl di It may be isocyanate (4,4'-methylenediphenyl diisocyanate).

According to one embodiment, in Formula 1, n may be an integer of 2 to 1,000, preferably an integer of 2 to 500, more preferably an integer of 5 to 100, more preferably an integer of 11 to 40, Even more preferably, it may be an integer of 15 to 35. In Formula 1, when the value of n is too low, the low-temperature impact resistance of the copolymer may be reduced, and when the value of n is too high, the transparency of the copolymer may be reduced.

According to one embodiment, the number average molecular weight of the polysiloxane of Formula 1 may be 500 to 15,000, preferably 3,000 to 6,000, but is not limited thereto.

(B) hydroxy terminated polysiloxane of formula (2)

The hydroxy-terminated polysiloxane represented by the following formula (2) included as a repeating unit in the polysiloxane-polycarbonate copolymer according to the present invention is a hydroxy-terminated polysiloxane compound having a hydroxyphenyl group at the terminal.

[Formula 2]

In Formula 2,

R ₁ each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group or an aryl group,

R ₂ each independently represents a hydrocarbon group or a hydroxyl group having 1 to 13 carbon atoms,

R ₃ each independently represents an alkylene group having 2 to 8 carbon atoms,

l represents an integer of 0 to 4,

m each independently represents an integer of 2 to 1,000.

According to one embodiment, in Formula 2,

R ₁ each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

R ₂ each independently represents a hydrocarbon group or a hydroxyl group having 1 to 13 carbon atoms,

R ₃ each independently represents an alkylene group having 2 to 8 carbon atoms,

l represents an integer of 0 to 4,

m each independently represents an integer of 2 to 1,000.

More specifically,

In R ₁ of Formula 2, the halogen atom may be Cl or Br; The alkyl group may be an alkyl group having 1 to 13 carbon atoms, such as methyl, ethyl or propyl; The alkoxy group may be an alkoxy group having 1 to 13 carbon atoms, such as methoxy, ethoxy or propoxy; The aryl group may be an aryl group having 6 to 10 carbon atoms, such as phenyl, chlorophenyl or tolyl;

In R ₂ of Formula 2, the hydrocarbon group having 1 to 13 carbon atoms is an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, an alkenyl group having 2 to 13 carbon atoms, an alkenyloxy group having 2 to 13 carbon atoms, 3 to carbon atoms. A cycloalkyl group of 6, a cycloalkoxy group of 3 to 6 carbons, an aryloxy group of 6 to 10 carbons, an aralkyl group of 7 to 13 carbons, an aralkoxy group of 7 to 13 carbons, an alkaryl group of 7 to 13 carbons, or a carbon number It may be an alkaryloxy group of 7 to 13.

According to one embodiment, the hydroxy-terminated polysiloxane of Formula 2 is prepared by using, for example, a compound of Formula 2a below having a hydroxyl group and a double bond and a compound of Formula 2b below containing silicon using a platinum-based catalyst. : It can be prepared by synthesizing in a molar ratio of 1.

[Formula 2a]

In Formula 2a, R ₁ and 1 are as defined in Formula 2 above, and k represents an integer of 1 to 7.

[Formula 2b]

In Formula 2b, R ₂ and m are the same as defined in Formula 2 above.

According to one embodiment, in Formula 2, m may be an integer of 2 to 1,000, preferably an integer of 2 to 500, more preferably an integer of 5 to 100, more preferably an integer of 20 to 80, Even more preferably, it may be an integer of 30 to 75. In the polysiloxane of Formula 2, when the value of m is too low, the low-temperature impact resistance of the copolymer may decrease, and when the value of m is too high, the transparency of the copolymer may decrease.

According to one embodiment, the number average molecular weight of the polysiloxane of Formula 2 may be 500 to 15,000, preferably 2,500 to 6,000, but is not limited thereto.

(C) polycarbonate block

The polysiloxane-polycarbonate copolymer according to the present invention includes a polycarbonate block as a repeating unit together with the hydroxy-terminated polysiloxane of Formula 1 and the hydroxy-terminated polysiloxane of Formula 2 above.

In one embodiment, the polycarbonate block may have a structure represented by the following Chemical Formula 3:

[Formula 3]

In Formula 3,

R ₄ is an alkyl group (eg, an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 13 carbon atoms), a cycloalkyl group (eg, a cycloalkyl group having 3 to 20 carbon atoms, preferably 3 to 6 carbon atoms), an alkenyl group (eg, An alkenyl group having 2 to 20 carbon atoms, preferably an alkenyl group having 2 to 13 carbon atoms), an alkoxy group (eg, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 13 carbon atoms), a halogen atom (eg Cl or Br) or nitro represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, substituted or unsubstituted with a group.

According to one embodiment, the aromatic hydrocarbon group of R ₄ of Formula 3 may be, for example, derived from the compound of Formula 4 below.

[Formula 4]

In Formula 4,

L is a straight, branched or cyclic alkylene group having no functional group; Or a straight, branched or cyclic alkylene group containing at least one functional group selected from the group consisting of or a sulfide group, an ether group, a sulfoxide group, a sulfone group, a ketone group, a naphthyl group, or an isobutylphenyl group (eg, having 1 to 10 carbon atoms) of a linear alkylene group, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms);

R ₅ and R ₆ are each independently a halogen atom (eg, Cl or Br, etc.); or a straight, branched or cyclic alkyl group (eg, a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms);

p and q each independently represent the integer of 0-4.

Specifically, the compound of Formula 4 is, for example, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)naphthylmethane, bis(4- Hydroxyphenyl)-(4-isobutylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1-ethyl-1,1-bis(4-hydroxyphenyl)propane, 1-phenyl- 1,1-bis(4-hydroxyphenyl)ethane, 1-naphthyl-1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, 1,10 -bis(4-heed

Roxyphenyl)decane, 2-methyl-1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane , 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) nonane, 2,2-bis (3 -methyl-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 4-methyl-2,2-bis (4-hydroxyphenyl) pentane, 4, 4-bis (4-hydroxyphenyl) heptane, diphenyl-bis (4-hydroxyphenyl) methane, resorcinol, hydroquinone, 4,4'-dihydroxyphenyl ether [bis (4-hydroxyphenyl) ether], 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5-dichloro-4-hydroxyphenyl) ether, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4- Dihydroxy-3-methylbenzene, 4,4'-dihydroxydiphenol [p,p'-dihydroxyphenyl], 3,3'-dichloro-4,4'-dihydroxyphenyl, 1, 1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dichloro-4-hydro Roxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1-bis( 4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)decane, 1,4-bis(4-hydroxyphenyl)propane, 1,4-bis(4-hydroxyphenyl)butane, 1,4-bis(4-hydroxyphenyl)isobutane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, bis(3 , 5-dimethyl-4-hydroxyphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2 ,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,4-bis (4-hydroxy Roxyphenyl)-2-methyl-butane, 4,4'-thio Diphenol [bis (4-hydroxyphenyl) sulfone], bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3-chloro-4-hydroxyphenyl) sulfone, bis (4-hydroxy Phenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(3-methyl-4-hydroxyphenyl)sulfide, bis(3,5-dimethyl-4-hydroxyphenyl)sulfide, bis(3,5 -dibromo-4-hydroxyphenyl) sulfoxide, 4,4'-dihydroxybenzophenone, 3,3',5,5'-tetramethyl-4,4'-dihydroxybenzophenone, 4 ,4'-dihydroxy diphenyl, methylhydroquinone, 1,5-dihydroxynaphthalene, or 2,6-dihydroxynaphthalene may be selected from, but not necessarily limited to. A typical example is 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). Other functional dihydric phenols (dihydric phenol) may refer to US Pat. Nos. 2,999,835, US 3,028,365, US 3,153,008, and US 3,334,154, and the like, and the dihydric phenols are singly or in combination of two or more. can be used

As another monomer of the polycarbonate block, a carbonate precursor, for example, carbonyl chloride (phosgene), carbonyl bromide, bis halo formate, diphenyl carbonate, or dimethyl carbonate may be used.

(D) polysiloxane-polycarbonate copolymer

The polysiloxane-polycarbonate copolymer of the present invention comprises, as repeating units, a hydroxyl-terminated polysiloxane of Formula 1, a hydroxyl-terminated polysiloxane of Formula 2, and a polycarbonate block, as described above, wherein the hydroxyl-terminated polysiloxane of Formulas 1 and 2 A total of 100 parts by weight of the polysiloxanes consists of 1 to 39 parts by weight of the polysiloxane of the formula (1) and 61 to 99 parts by weight of the polysiloxane of the formula (2).

When the content of the polysiloxane of Formula 1 in the total of 100 parts by weight of the hydroxy-terminated polysiloxanes of Formulas 1 and 2 is less than 1 part by weight (or when the polysiloxane content of Formula 2 exceeds 99 parts by weight), the transparency of the resulting copolymer is lowered Conversely, when the polysiloxane content of Formula 1 exceeds 39 parts by weight (or when the polysiloxane content of Formula 2 is less than 61 parts by weight), the overall production yield of polysiloxane may be reduced.

In one embodiment, the polysiloxane content of Formula 1 in a total of 100 parts by weight of the hydroxy-terminated polysiloxanes of Formulas 1 and 2 is 1.5 parts by weight or more, 2 parts by weight or more, 2.5 parts by weight or more, 3 parts by weight or more, 3.5 parts by weight or more. parts by weight or more, 4 parts by weight or more, 4.5 parts by weight or more, or 5 parts by weight or more, and also 38 parts by weight or less, 37 parts by weight or less, 36 parts by weight or less, 35 parts by weight or less, 34 parts by weight or less, 33 parts by weight or less , 32 parts by weight or less, 31 parts by weight or less, or 30 parts by weight or less.

In one embodiment, the polysiloxane content of Formula 2 in a total of 100 parts by weight of the hydroxy-terminated polysiloxanes of Formulas 1 and 2 is 62 parts by weight or more, 63 parts by weight or more, 64 parts by weight or more, 65 parts by weight or more, 66 parts by weight or more. parts by weight or more, 67 parts by weight or more, 68 parts by weight or more, 69 parts by weight or more, or 70 parts by weight or more, and also 98.5 parts by weight or less, 98 parts by weight or less, 97.5 parts by weight or less, 97 parts by weight or less, 96.5 parts by weight or less , 96 parts by weight or less, 95.5 parts by weight or less, or 95 parts by weight or less.

In one embodiment, the total content of the polysiloxane of Formula 1 and the polysiloxane of Formula 2 included as a repeating unit in the polysiloxane-polycarbonate copolymer of the present invention may be 3 to 39% by weight based on the total weight of the copolymer, and more Specifically, it may be 4 to 30% by weight, more specifically 4 to 25% by weight, and still more specifically 4 to 20% by weight. When the total content of the polysiloxane of Formula 1 and the polysiloxane of Formula 2 is less than 3% by weight based on the total weight of the copolymer, the low-temperature impact resistance of the copolymer may decrease, and when it exceeds 39% by weight, the copolymer Fluidity may be reduced, making extrusion or injection processing difficult.

In one embodiment, the polysiloxane-polycarbonate copolymer according to the present invention has a viscosity average molecular weight of 13,000 to 69,000, more specifically 14,000 to 65,000, even more specifically 15,000 to 60,000, even more specifically 16,000 to 55,000, More specifically, it may be 16,000 to 50,000, and even more specifically, 16,000 to 45,000. When the viscosity average molecular weight of the copolymer is too low, mechanical properties including low-temperature impact resistance may be reduced. can be difficult

In one embodiment, the content of the polycarbonate block in the polysiloxane-polycarbonate copolymer of the present invention may be 61 to 97% by weight, more specifically 70 to 96% by weight, even more specifically, based on the total weight of the copolymer. It may be 75 to 96% by weight, more specifically 80 to 96% by weight. If the content of the polycarbonate block is less than 61% by weight, transparency and processability of the copolymer may be reduced, and if the content of the polycarbonate block exceeds 97% by weight, the low-temperature impact resistance of the copolymer may be reduced.

The polysiloxane-polycarbonate copolymer of the present invention is prepared by reacting (1) the hydroxyl-terminated polysiloxane of Formula 1, the hydroxyl-terminated polysiloxane of Formula 2, and the oligomeric polycarbonate under interfacial reaction conditions to form a polysiloxane-polycarbonate intermediate to do; and (2) polymerizing the polysiloxane-polycarbonate intermediate using a first polymerization catalyst; 1 to 39 parts by weight of the polysiloxane of 1 and 61 to 99 parts by weight of the polysiloxane of the formula (2).

In one embodiment, the (1) polysiloxane-forming the polycarbonate intermediate comprises a mixture content of the polysiloxane of Formula 1 and the polysiloxane of Formula 2 and an oligomeric polycarbonate content of 3:97 to 39:61, more specifically may include mixing in a weight ratio of 4:96 to 30:70, more specifically 4:96 to 25:75, and still more specifically 4:96 to 20:80.

In one embodiment, the polysiloxane-polycarbonate used in the preparation of the polycarbonate copolymer according to the present invention may be an oligomeric polycarbonate having a viscosity average molecular weight of 800 to 20,000, more specifically, 1,000 to 15,000. If the viscosity average molecular weight of the polycarbonate is less than 800, the molecular weight distribution of the copolymer may be widened and physical properties may be deteriorated, and if it exceeds 20,000, the reactivity may be reduced.

In one embodiment, the oligomeric polycarbonate is prepared by adding the above-mentioned dihydric phenol compound to an aqueous alkali solution to make a phenol salt state, and then reacting the phenols in the salt state into dichloromethane injected with phosgene gas to react. . For the preparation of polycarbonate oligomers, it is desirable to maintain the molar ratio of phosgene to dihydric phenols (eg, bisphenol A) in the range of about 1:1 to 1.5:1, more preferably about 1:1 to 1.2:1. desirable. If the molar ratio of phosgene to the dihydric phenol compound is less than 1, the reactivity may decrease, and if the molar ratio of phosgene to the dihydric phenol compound exceeds 1.5, processability may occur due to excessive molecular weight increase.

The polycarbonate oligomer formation reaction may be generally performed at a temperature in the range of about 15 to 60° C., and an alkali metal hydroxide (eg, sodium hydroxide) may be used to adjust the pH of the reaction mixture.

In one embodiment, the step of (1) polysiloxane-forming the polycarbonate intermediate comprises forming a mixture comprising the polysiloxane of Formula 1, the polysiloxane of Formula 2, and the oligomeric polycarbonate, the mixture It may also include a silver phase transfer catalyst, a molecular weight modifier, and a second polymerization catalyst.

In one embodiment, the (1) polysiloxane-forming the polycarbonate intermediate comprises: forming a mixture comprising the polysiloxane of Formula 1, the polysiloxane of Formula 2, and an oligomeric polycarbonate; and extracting the organic phase from the resulting mixture after the reaction of the polysiloxane of Formula 1, the polysiloxane of Formula 2, and the oligomeric polycarbonate is completed, wherein (2) the polysiloxane-polymerizing the polycarbonate intermediate comprises: 1 may include providing a polymerization catalyst to the extracted organic phase.

Specifically, the polysiloxane-polycarbonate copolymer according to the present invention is prepared by adding the polysiloxane of Formula 1 and the polysiloxane of Formula 2 described above to an organic phase-aqueous mixture containing polycarbonate, and adding a molecular weight modifier and a catalyst in stages. can

As the molecular weight control agent, a monofunctional compound similar to a monomer used for preparing polycarbonate may be used. Monofunctional substances include, for example, p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumylphenol, p-isooctylphenol, and p-isononyl. phenol-based derivatives such as phenol and the like; or aliphatic alcohols. Preferably, p-tert-butylphenol (PTBP) can be used.

A polymerization catalyst and/or a phase transfer catalyst may be used as the catalyst. As the polymerization catalyst, for example, triethylamine (TEA) may be used, and as the phase transfer catalyst, for example, a compound of Formula 5 below may be used.

[Formula 5]

(R ₇ ) ₄ Q ⁺ X ^-

In Formula 5, R ₇ represents an alkyl group having 1 to 10 carbon atoms, Q represents nitrogen or phosphorus, and X represents a halogen atom or —OR ₈ . Here, R ₈ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.

Specifically, the phase transfer catalyst is, for example, [CH ₃ (CH ₂ ) ₃ ] ₄ NX, [CH ₃ (CH ₂ ) ₃ ] ₄ PX, [CH ₃ (CH ₂ ) ₅ ] ₄ NX, [CH ₃ ( CH ₂ ) ₆ ] ₄ NX, [CH ₃ (CH ₂ ) ₄ ] ₄ NX, CH ₃ [CH ₃ (CH ₂ ) ₃ ] ₃ NX or CH ₃ [CH ₃ (CH ₂ ) ₂ ] ₃ NX . In the above formulas, X represents Cl, Br or -OR ₉ , where R ₉ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.

The content of the phase transfer catalyst is preferably about 0.01 to 10% by weight based on the total weight of the mixture of the polysiloxane of Formula 1, the polysiloxane of Formula 2, and the oligomeric polycarbonate. If the content is less than 0.01% by weight, the reactivity may be reduced, and if the content exceeds 10% by weight, it may precipitate as a precipitate or the transparency may be deteriorated.

In a preferred embodiment, after preparing the polysiloxane-polycarbonate copolymer, the organic phase dispersed in methylene chloride may be separated after alkali washing. Subsequently, the organic phase may be washed with a 0.1N hydrochloric acid solution, and then washed with distilled water 2 to 3 times. When washing is complete, the concentration of the organic phase dispersed in methylene chloride is adjusted to be constant, and granulation can be performed using a certain amount of pure water in the range of 70 to 80°C. If the temperature of the pure water is less than 70 ℃, the assembly speed is slow, the assembly time may be very long, and if the temperature of the pure water exceeds 80 ℃, it may be difficult to obtain the shape of the polycarbonate in a certain size. When granulation is completed, it is preferable to firstly dry at 100 to 110°C for 5 to 10 hours, and secondly at 110 to 120°C for 5 to 10 hours.

The polysiloxane-polycarbonate copolymer according to the present invention is excellent in transparency and low-temperature impact resistance at the same time, so it can be usefully used in the production of film and sheet products, such as housings for office equipment and electrical and electronic products.

Accordingly, according to another aspect of the present invention, there is provided a molded article including the polysiloxane-polycarbonate copolymer of the present invention.

The method for preparing a molded article by molding the polysiloxane-polycarbonate copolymer of the present invention is not particularly limited, and a molded article may be manufactured using a method generally used in the plastic molding field.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited thereto.

[Example]

<Preparation of hydroxy-terminated polysiloxane>

Preparation Example 1: Preparation of hydroxy-terminated polysiloxane of Formula 1 having an ester bond

In a 100 mL three-neck flask equipped with a condenser, 0.03 mol of 2-allylphenol and 0.015 mol of hydride terminated polydimethylsiloxane were completely dissolved in 50 mL of chlorobenzene under a nitrogen atmosphere. 0.00364 mmol of a platinum-based catalyst (platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex) was added and refluxed for 24 hours. After that, the solvent of the reaction solution was removed and washed with distilled water. Thereafter, by drying in a vacuum oven for 24 hours, a hydroxy-terminated polysiloxane of the following formula (A) was prepared. At this time, by controlling the number average molecular weight of the hydride-terminated polydimethylsiloxane, hydroxy-terminated polysiloxanes of the following formula A having various number average molecular weights were prepared.

In a 500 mL three-neck flask equipped with a condenser, 0.04 mol of the hydroxy-terminated polysiloxane of the following formula A was dissolved in 300 mL of chloroform under a nitrogen atmosphere, and then 67 mL of triethylamine (TEA) was added. While the solution was refluxed, 0.020 mol of terephthaloyl chloride was dissolved in 100 mL of chloroform, and then slowly added to the solution for 1 hour and refluxed for 12 hours. After removing the solvent of the reaction solution, it was dissolved in acetone and washed with hot distilled water. Thereafter, by drying in a vacuum oven for 24 hours, a hydroxy-terminated polysiloxane having an ester bond of the following formula (B) was prepared.

[Formula A]

[Formula B]

In Formulas A and B, n each independently represents an integer of 15 to 34.

Preparation Example 2: Preparation of hydroxy-terminated polysiloxane of Formula 2

In a 100 mL three-neck flask equipped with a condenser, 0.03 mol of 2-allylphenol and 0.015 mol of hydride terminated polydimethylsiloxane were completely dissolved in 50 mL of chlorobenzene under a nitrogen atmosphere. 0.00364 mmol of a platinum-based catalyst (platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex) was added and refluxed for 24 hours. After that, the solvent of the reaction solution was removed and washed with distilled water. Thereafter, by drying in a vacuum oven for 24 hours, a hydroxy-terminated polysiloxane of the following formula (C) was prepared. At this time, by controlling the number average molecular weight of the hydride-terminated polydimethylsiloxane, a hydroxy-terminated polysiloxane of the following formula C having various number average molecular weights was prepared.

[Formula C]

In Formula C, m represents an integer of 30 to 70.

Preparation Example 3: Preparation of hydroxy-terminated polysiloxane of Formula 1 having a urethane bond

In a 100 mL three-neck flask equipped with a condenser, 0.08 mol of 2-allylphenol and 0.04 mol of hydride terminated polydimethylsiloxane were completely dissolved in 50 mL of chlorobenzene under a nitrogen atmosphere, and then 0.00364 mmol of a platinum-based catalyst (platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex) was added and refluxed for 24 hours. After that, the solvent of the reaction solution was removed and washed with distilled water. Thereafter, the hydroxy terminated polysiloxane was prepared by drying in a vacuum oven for 24 hours. At this time, by controlling the number average molecular weight of the hydride-terminated polydimethylsiloxane, a hydroxy-terminated polysiloxane of the following formula D having various number average molecular weights was prepared.

In a 500 mL three-neck flask equipped with a condenser, 0.04 mol of the hydroxy-terminated polysiloxane of the following formula (D) was dissolved in 200 mL of chloroform under a nitrogen atmosphere to prepare a solution. While the solution was refluxed, 0.02 mol of 1,4-phenylenediisocyanate was dissolved in 50 mL of chloroform, and then the solution was maintained at 60° C. using a dropping funnel for 1 hour. Slowly added. After adding a small amount of triethylenediamine (TEDA) to the mixed solution, it was refluxed for 24 hours. After the solvent was removed from the reaction solution, it was washed with hot distilled water. Thereafter, by drying in a vacuum oven for 24 hours, a hydroxy-terminated polysiloxane having a urethane bond of the following formula E was prepared.

[Formula D]

[Formula E]

In Formulas D and E, o each independently represents an integer of 15 to 34.

<Preparation of polysiloxane-polycarbonate copolymer>

Example 1

Bisphenol A and phosgene gas in an aqueous solution were subjected to an interfacial reaction in the presence of methylene chloride to prepare 1 L of an oligomeric polycarbonate mixture having a viscosity average molecular weight of about 1000. Polysiloxane mixture of the polysiloxane of formula B obtained in Preparation Example 1 (n=30) obtained in Preparation Example 1 (n=30) dissolved in methylene chloride and the polysiloxane of Formula C (m=35) obtained in Preparation Example 2 in a weight ratio of 10:90 ( Based on the total weight of the copolymer, 5% by weight of a polysiloxane mixture), 1.8 mL of tetrabutylammonium chloride (TBACl), 2.61 g of p-tert-butylphenol (PTBP) and Triethylamine , TEA) 186 μL, was mixed with the obtained oligomeric polycarbonate mixture and reacted for 30 minutes. The reacted mixture was subjected to stationary separation, and after layer separation occurred, only the organic phase was collected, and 170 g of sodium hydroxide aqueous solution, 370 g of methylene chloride and 23 μL of triethylamine were mixed thereto and reacted for 2 hours. After separation of the layers, water was added to the organic phase having increased viscosity and separated. Subsequently, the organic phase was washed with 0.1N hydrochloric acid solution, and then washed with distilled water 2 to 3 times. After washing was completed, the concentration of the organic phase was constant at 76° C. and solidified using a certain amount of pure water. After solidification was completed, the polysiloxane-polycarbonate copolymer was prepared by firstly drying at 110° C. for 8 hours, and secondly drying at 120° C. for 10 hours. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and shown in Table 1 below.

Example 2

The number average molecular weight of the polysiloxane of Formula B obtained in Preparation Example 1, the number average molecular weight of the polysiloxane of Formula C obtained in Preparation Example 2, the polysiloxane of Formula B obtained in Preparation Example 1 and Formula C obtained in Preparation Example 2 The weight ratio of the polysiloxane, and the content of the mixture of the polysiloxane of Formula B obtained in Preparation Example 1 and the polysiloxane of Formula C obtained in Preparation Example 2 were changed as described in Table 1 below, and the content of p-tert-butylphenol was 2.61 A polysiloxane-polycarbonate copolymer was prepared in the same manner as in Example 1, except for changing from g to 2.24 g. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and shown in Table 1 below.

Example 3

The number average molecular weight of the polysiloxane of Formula B obtained in Preparation Example 1, the number average molecular weight of the polysiloxane of Formula C obtained in Preparation Example 2, the polysiloxane of Formula B obtained in Preparation Example 1 and Formula C obtained in Preparation Example 2 The same method as in Example 1, except that the weight ratio of the polysiloxane and the content of the mixture of the polysiloxane of Formula B obtained in Preparation Example 1 and the polysiloxane of Formula C obtained in Preparation Example 2 were changed as shown in Table 1 below. to prepare a polysiloxane-polycarbonate copolymer. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and shown in Table 1 below.

Example 4

The number average molecular weight of the polysiloxane of Formula B obtained in Preparation Example 1, the number average molecular weight of the polysiloxane of Formula C obtained in Preparation Example 2, the polysiloxane of Formula B obtained in Preparation Example 1 and Formula C obtained in Preparation Example 2 The weight ratio of the polysiloxane, and the content of the mixture of the polysiloxane of Formula B obtained in Preparation Example 1 and the polysiloxane of Formula C obtained in Preparation Example 2 were changed as described in Table 1 below, and the content of p-tert-butylphenol was 2.61 A polysiloxane-polycarbonate copolymer was prepared in the same manner as in Example 1, except for changing from g to 1.86 g. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and shown in Table 1 below.

Example 5

The number average molecular weight of the polysiloxane of Formula B obtained in Preparation Example 1, the number average molecular weight of the polysiloxane of Formula C obtained in Preparation Example 2, the polysiloxane of Formula B obtained in Preparation Example 1 and Formula C obtained in Preparation Example 2 The weight ratio of the polysiloxane, and the content of the mixture of the polysiloxane of Formula B obtained in Preparation Example 1 and the polysiloxane of Formula C obtained in Preparation Example 2 were changed as described in Table 1 below, and the content of p-tert-butylphenol was 2.61 A polysiloxane-polycarbonate copolymer was prepared in the same manner as in Example 1, except for changing from g to 1.49 g. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and shown in Table 1 below.

Example 6

The number average molecular weight of the polysiloxane of Formula B obtained in Preparation Example 1, the number average molecular weight of the polysiloxane of Formula C obtained in Preparation Example 2, the polysiloxane of Formula B obtained in Preparation Example 1 and Formula C obtained in Preparation Example 2 The weight ratio of the polysiloxane, and the content of the mixture of the polysiloxane of Formula B obtained in Preparation Example 1 and the polysiloxane of Formula C obtained in Preparation Example 2 were changed as described in Table 1 below, and the content of p-tert-butylphenol was 2.61 Except for changing from g to 3.36 g, it was carried out in the same manner as in Example 1 to prepare a polysiloxane-polycarbonate copolymer. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and shown in Table 1 below.

Example 7

The number average molecular weight of the polysiloxane of Formula B obtained in Preparation Example 1, the number average molecular weight of the polysiloxane of Formula C obtained in Preparation Example 2, the polysiloxane of Formula B obtained in Preparation Example 1 and Formula C obtained in Preparation Example 2 The weight ratio of the polysiloxane, and the content of the mixture of the polysiloxane of Formula B obtained in Preparation Example 1 and the polysiloxane of Formula C obtained in Preparation Example 2 were changed as described in Table 1 below, and the content of p-tert-butylphenol was 2.61 Except for changing from g to 2.98 g, it was carried out in the same manner as in Example 1 to prepare a polysiloxane-polycarbonate copolymer. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and shown in Table 1 below.

Example 8

Bisphenol A and phosgene gas in an aqueous solution were subjected to an interfacial reaction in the presence of methylene chloride to prepare 1 L of an oligomeric polycarbonate mixture having a viscosity average molecular weight of about 1000. A polysiloxane mixture obtained by mixing the polysiloxane of formula E obtained in Preparation Example 3 (o=30) and the polysiloxane of Formula C (m=35) obtained in Preparation Example 2 (m=35) dissolved in methylene chloride in a weight ratio of 10:90 ( Based on the total weight of the copolymer, 5% by weight of a polysiloxane mixture), 1.8 mL of tetrabutylammonium chloride (TBACl), 2.61 g of p-tert-butylphenol (PTBP) and Triethylamine , TEA) 186 μL, was mixed with the obtained oligo parent polycarbonate mixture and reacted for 30 minutes. The reacted mixture was subjected to stationary separation, and after layer separation occurred, only the organic phase was collected, and 170 g of sodium hydroxide aqueous solution, 370 g of methylene chloride and 23 μL of triethylamine were mixed thereto and reacted for 2 hours. After separation of the layers, water was added to the organic phase having increased viscosity and separated. Subsequently, the organic phase was washed with 0.1N hydrochloric acid solution, and then washed with distilled water 2 to 3 times. After washing was completed, the concentration of the organic phase was constant at 76° C. and solidified using a certain amount of pure water. After solidification was completed, the polysiloxane-polycarbonate copolymer was prepared by firstly drying at 110° C. for 8 hours, and secondly drying at 120° C. for 10 hours. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and shown in Table 1 below.

Example 9

The number average molecular weight of the polysiloxane of Formula E obtained in Preparation Example 3, the number average molecular weight of the polysiloxane of Formula C obtained in Preparation Example 2, the polysiloxane of Formula E obtained in Preparation Example 3 and Formula C obtained in Preparation Example 2 The weight ratio of polysiloxane, and the content of the mixture of the polysiloxane of Formula E obtained in Preparation Example 3 and the polysiloxane of Formula C obtained in Preparation Example 2 were changed as described in Table 1 below, and the content of p-tert-butylphenol was 2.61 A polysiloxane-polycarbonate copolymer was prepared in the same manner as in Example 8, except for changing from g to 3.12 g. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and shown in Table 1 below.

[Table 1]

Comparative Example 1

The number average molecular weight of the polysiloxane of Formula B obtained in Preparation Example 1, the number average molecular weight of the polysiloxane of Formula C obtained in Preparation Example 2, the polysiloxane of Formula B obtained in Preparation Example 1 and Formula C obtained in Preparation Example 2 The weight ratio of polysiloxane, and the content of the mixture of the polysiloxane of Formula B obtained in Preparation Example 1 and the polysiloxane of Formula C obtained in Preparation Example 2 were changed as described in Table 2 below, and the content of p-tert-butylphenol was 2.61 A polysiloxane-polycarbonate copolymer was prepared in the same manner as in Example 1, except for changing from g to 1.49 g. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and shown in Table 2 below.

Comparative Example 2

The number average molecular weight of the polysiloxane of Formula B obtained in Preparation Example 1, the number average molecular weight of the polysiloxane of Formula C obtained in Preparation Example 2, the polysiloxane of Formula B obtained in Preparation Example 1 and Formula C obtained in Preparation Example 2 The weight ratio of polysiloxane, and the content of the mixture of the polysiloxane of Formula B obtained in Preparation Example 1 and the polysiloxane of Formula C obtained in Preparation Example 2 were changed as described in Table 2 below, and the content of p-tert-butylphenol was 2.61 Except for changing from g to 2.98 g, it was carried out in the same manner as in Example 1 to prepare a polysiloxane-polycarbonate copolymer. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and shown in Table 2 below.

Comparative Example 3

The number average molecular weight of the polysiloxane of Formula B obtained in Preparation Example 1, the number average molecular weight of the polysiloxane of Formula C obtained in Preparation Example 2, the polysiloxane of Formula B obtained in Preparation Example 1 and Formula C obtained in Preparation Example 2 The weight ratio of polysiloxane, and the content of the mixture of the polysiloxane of Formula B obtained in Preparation Example 1 and the polysiloxane of Formula C obtained in Preparation Example 2 were changed as described in Table 2 below, and the content of p-tert-butylphenol was 2.61 A polysiloxane-polycarbonate copolymer was prepared in the same manner as in Example 1, except that g was changed to 2.95 g. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and shown in Table 2 below.

Comparative Example 4

The number average molecular weight of the polysiloxane of Formula B obtained in Preparation Example 1, the number average molecular weight of the polysiloxane of Formula C obtained in Preparation Example 2, the polysiloxane of Formula B obtained in Preparation Example 1 and Formula C obtained in Preparation Example 2 The weight ratio of polysiloxane, and the content of the mixture of the polysiloxane of Formula B obtained in Preparation Example 1 and the polysiloxane of Formula C obtained in Preparation Example 2 were changed as described in Table 2 below, and the content of p-tert-butylphenol was 2.61 A polysiloxane-polycarbonate copolymer was prepared in the same manner as in Example 1, except for changing from g to 1.86 g. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and shown in Table 2 below.

[Table 2]

The physical properties of Tables 1 and 2 were measured by the following method.

1) The overall production yield of polysiloxane was calculated by the following formula.

[Total weight of polysiloxane actually produced (g)/total weight of polysiloxane obtained theoretically (g)] x 100 (%)

2) Viscosity average molecular weight (Mv): The viscosity of the methylene chloride solution was measured at 20° C. using an Ubbelohde Viscometer, and the intrinsic viscosity [η] was calculated from this using the following formula.

[η]=1.23 x 10 ^-5 Mv ^0.83

3) Transmittance (%): The transmittance was measured using a haze meter (HAZE-GARD PLUS manufactured by BYK GARDNER).

4) Low-temperature impact strength: Based on ASTM D256, each specimen of Examples and Comparative Examples was notched and evaluated under a low-temperature condition of -40°C. Specifically, 10 low-temperature impact strength measurements were performed for each specimen, and the average value of the 10 measurements was calculated.

- Ductile: No separation of the specimen when measuring low-temperature impact strength

- Brittle: Separation of the specimen occurs when measuring impact strength at low temperature

As shown in Table 1, in the case of the copolymers of Examples 1 to 9 according to the present invention, the transmittance was 85% or more, which was excellent in transparency, and the overall production yield of polysiloxane was very excellent as 90% or more, and the low temperature resistance was excellent. Impact properties were also excellent.

However, as shown in Table 2, in the case of the copolymer of Comparative Example 1 using the polysiloxane of Formula 2 alone as the polysiloxane, the transmittance was 82% and the transparency was poor, and Comparative Example 2 using the polysiloxane of Formula 1 alone as the polysiloxane In the case of the copolymer, the production yield of the entire polysiloxane was poor at 81%.

In addition, even when a mixture of the polysiloxane of Formula 1 and the polysiloxane of Formula 2 was used as the polysiloxane, the transmittance of the copolymer of Comparative Example 3 was 83%, and the transparency was poor, and in the case of the copolymer of Comparative Example 4, the production yield of the entire polysiloxane and poor transparency, and particularly, very poor low-temperature impact resistance.

Claims (13)

As the repeating unit, a hydroxy-terminated polysiloxane represented by the following formula (1); Hydroxy-terminated polysiloxane of Formula 2; and a polycarbonate block;
wherein 100 parts by weight in total of the hydroxy-terminated polysiloxanes of Formulas 1 and 2 consist of 3 to 30 parts by weight of the polysiloxane of Formula 1 and 70 to 97 parts by weight of the polysiloxane of Formula 2,
Polysiloxane-Polycarbonate Copolymer:
[Formula 1]

[Formula 2]

In Formulas 1 and 2,
R ₁ each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group or an aryl group,
R ₂ each independently represents a hydrocarbon group or a hydroxyl group having 1 to 13 carbon atoms,
R ₃ each independently represents an alkylene group having 2 to 8 carbon atoms,
A represents a substituted or unsubstituted divalent hydrocarbon group containing at least one bond selected from an ester bond, an ether bond, a thioether bond, a ketone bond, or a urethane bond,
l represents an integer of 0 to 4,
m and n each independently represent an integer of 2 to 1,000. According to claim 1, in Formulas 1 and 2,
R ₁ each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
R ₂ each independently represents a hydrocarbon group or a hydroxyl group having 1 to 13 carbon atoms,
R ₃ each independently represents an alkylene group having 2 to 8 carbon atoms,
A is

, wherein Y is X or NH-X-NH, wherein X is a linear or branched aliphatic group having 1 to 20 carbon atoms; a cycloalkylene group having 3 to 20 carbon atoms; or a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms, which is substituted or unsubstituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a carboxyl group,
l represents an integer of 0 to 4,
m and n each independently represent an integer from 2 to 1,000,
Polysiloxane-polycarbonate copolymer. The polysiloxane-polycarbonate copolymer according to claim 1, wherein in Formula 1, n is an integer of 11 to 40, and in Formula 2, m is an integer of 20 to 80. The polysiloxane-polycarbonate copolymer according to claim 1, wherein the polycarbonate block has a structure represented by the following formula (3):
[Formula 3]

In Formula 3,
R ₄ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, substituted or unsubstituted with an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a halogen atom or a nitro group. The polysiloxane-polycarbonate copolymer according to claim 4, wherein the aromatic hydrocarbon group of R ₄ of Formula 3 is derived from a compound of Formula 4 below:
[Formula 4]

In Formula 4,
L is a straight, branched or cyclic alkylene group having no functional group; or a straight, branched or cyclic alkylene group comprising at least one functional group selected from the group consisting of a sulfide group, an ether group, a sulfoxide group, a sulfone group, a ketone group, a naphthyl group or an isobutylphenyl group,
R ₅ and R ₆ are each independently a halogen atom; or a straight, branched or cyclic alkyl group,
p and q each independently represent the integer of 0-4. The polysiloxane-polycarbonate copolymer according to claim 1, wherein the total content of the hydroxy-terminated polysiloxane of Formula 1 and the hydroxy-terminated polysiloxane of Formula 2 is 3 to 39 wt% based on the total weight of the polysiloxane-polycarbonate copolymer. The polysiloxane-polycarbonate copolymer according to claim 1, wherein the polysiloxane-polycarbonate copolymer has a viscosity average molecular weight of 13,000 to 69,000. (1) reacting a hydroxy-terminated polysiloxane of Formula 1, a hydroxyl-terminated polysiloxane of Formula 2, and an oligomeric polycarbonate under interfacial reaction conditions to form a polysiloxane-polycarbonate intermediate; and
(2) polymerizing the polysiloxane-polycarbonate intermediate using a first polymerization catalyst;
wherein 100 parts by weight in total of the hydroxy-terminated polysiloxanes of Formulas 1 and 2 consist of 3 to 30 parts by weight of the polysiloxane of Formula 1 and 70 to 97 parts by weight of the polysiloxane of Formula 2,
Method for preparing polysiloxane-polycarbonate copolymer:
[Formula 1]

[Formula 2]

In Formulas 1 and 2,
R ₁ each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group or an aryl group,
R ₂ each independently represents a hydrocarbon group or a hydroxyl group having 1 to 13 carbon atoms,
R ₃ each independently represents an alkylene group having 2 to 8 carbon atoms,
A represents a substituted or unsubstituted divalent hydrocarbon group containing at least one bond selected from an ester bond, an ether bond, a thioether bond, a ketone bond, or a urethane bond,
l represents an integer of 0 to 4,
m and n each independently represent an integer of 2 to 1,000. The method according to claim 8, wherein the (1) polysiloxane-forming polycarbonate intermediate comprises a mixture content of the hydroxy-terminated polysiloxane of Formula 1 and the hydroxy-terminated polysiloxane of Formula 2 and an oligomeric polycarbonate content of 3:97 to A method for producing a polysiloxane-polycarbonate copolymer, comprising mixing in a weight ratio of 39:61. The method of claim 8, wherein (1) forming the polysiloxane-polycarbonate intermediate comprises the step of forming a mixture comprising the hydroxyl-terminated polysiloxane of Formula 1, the hydroxyl-terminated polysiloxane of Formula 2, and the oligomeric polycarbonate wherein the mixture further comprises a phase transfer catalyst, a molecular weight modifier and a second polymerization catalyst. 9. The method of claim 8,
The (1) polysiloxane-forming the polycarbonate intermediate may include: forming a mixture comprising a hydroxy-terminated polysiloxane of Formula 1, a hydroxyl-terminated polysiloxane of Formula 2, and an oligomeric polycarbonate; and extracting the organic phase from the resulting mixture after the reaction of the hydroxy-terminated polysiloxane of Formula 1, the hydroxy-terminated polysiloxane of Formula 2, and the oligomeric polycarbonate is completed,
The step of (2) polymerizing the polysiloxane-polycarbonate intermediate comprises providing a first polymerization catalyst to the extracted organic phase,
A method for preparing a polysiloxane-polycarbonate copolymer. The method of claim 8, wherein the oligomeric polycarbonate has a viscosity average molecular weight of 800 to 20,000. A molded article comprising the polysiloxane-polycarbonate copolymer according to any one of claims 1 to 7.